Process for producing heptachlor



. Patented Nov. 27, 1951 2,576,668 raocass roa raonocmo narraonnon Henry Bluestone and Rex Everett Lidov, Denver,

James Harvey Knaus,

William Howerton, Denver, Colo., asalgnors to Longmont, and Paul Julius Hyman & Company, Denver, Colo, a

corporation of Delaware No Drawing. Application Decemberl, 1949,

SerialNo. 131,692

12 Claims. (01. 280648) 1 This invention relates to new compositions of matter possessing unexpectedly high toxicity to insect life.

More specifically, this invention relates to a I new halogenated hydrocarbon composition possessing high insecticidal activity and it also relates to the methods of producing this new composition.

One object of this invention is to produce organic materials possessing a high order of insecticidal activity.

Another object of this invention is the production of a new insecticidally active organic composition for which the ratio of'insecticidal toxity to mammalian toxicity is relatively high.

A further object of this invention is to provide I means for producing this insecticidally active material both easily and economically.

Other objects, features, capabilities and advantages are comprehended by the invention, as will later appear and as I are inherently possessed thereby.

It has been known for some time that when the Diels-Alder addition compound resulting when one mole of hexachloro-cyclopentadiene is caused to react with one mole of cyclopentadiene (this .adduct will hereinafter be identified as HCA) is chlorinated a new substance possessing a remarkable degree of insecticidal activity is formed. The substance so obtained, now known as chlordane, is a light colored viscous liquid; it was disclosed and claimed in the co-pending application of Julius Hyman, Serial Number 607,078, filed July 25, 1945, and assigned to Velsicol Corporation, now abandoned. The liquid composition obtained by the procedures described in the cited application has the empirical formula -CioH6Cla. Chlordane would therefore appear to be the product obtained when one mole of chlorine is added to the aforementioned Diels-Alder adduct.

Continuing investigations of the liquid CinHsCls led to the significant discovery that this substance was not a single pure material but was instead a mixture of closely related compounds.

- These closely related compounds could be separated chromatographically and as a result there were obtained three pure crystalline compounds having the formulae CmHsClv, CioHcCla, and CmHsCls respectively. The CmHsCla compound thus obtained was found to be identical with a crystalline CioHsCla compound melting between 103 and 105 C. which is disclosed and claimed in U. S. Patent No. 2,519,190, issued to Julius Hyman on August 15, 1950, and assigned to Velsicol Corporation. This crystalline substance was found to have an insecticidal toxicity only about one-half that of the liquid material previously described.

The facts with respect to the crystalline comavail pound CroHeCla are disclosed and that compound is claimed in the co-pending application of Julius Hyman, Serial Number 736,419, filed March 21, 1947, and assigned to Julius Hyman 8; Company (now abandoned). Since the insecticidal activity of the compound C10H5C17 (now known as heptachlor) is approximately three and one-half to four times that of the liquid having the average composition of CioHaCla the much higher activity of this liquid as compared with the crystalline CmHsCla was adequately explained.

Since the time of the original disclosure of the hereinabove recited facts the adduct HCA has been chlorinated many times under a variety of conditions and in a variety of solvents. This procedure, when neither a deficiency nor an excess of chlorine was used, has invariably led to the normally expected product, that is, either the active liquid CmHcCla or the less active crystalline CioHsCls.

More recently, Bluestone, Tajima and Lidov in a co-pending application, Serial Number 131,061, filed December 3, 1949, have disclosed that chlorination of the adduct HCA dissolved in benzene and chlorinated in the complete absence of light gives rise to a hitherto unknown isomer having the empirical formula CmHsCla. These applicants also show that the yield of this isomer can be appreciably increased by carrying out the chicrination in the presence of finely divided carbon or by making other modifications in the chlorination process. This new CroHcClc isomerwhich .tive insect toxicant than the first known crystalline CinHeCla isomer which now has been designated a-ODD. In this connection, it should be noted that theoretically the adduct'HC an, by the addition of two atoms of chlorineto I e double bond of the cyclopenteno ring, give rise'to four stereo-isomeric compounds which differ only in the relative spacial relationships of the two chlorine atoms to each other and to the remainder of the molecule of which they become a part. Of the four theoretically possible isomers thus obtainable only two have been isolated in pure form and are known to exist. As has just previously been noted they differ by a factor of approximately four in their insecticidal activity.

As might have been expected, the discovery that the crystalline compound C1oH5C17, which, when pure, melts between -96 C. possessed insect toxicity three and one-half to four times as great as that of the liquid CmHsCla mixture led inevitably to exhaustive research in an effort to find means for simply and economically making this desirable compound. As a result, indirect methods for its preparation have become le but none of these methods have the adv ntage of the simplicity which would beobtained if hepta-chlor could be prepared by direct 3 chlorination of the adduct HCA. However, until the present time all attempts to obtain the compound hep+a-chlor in this fashion have failed.

In general, no modification of the chlorination adduct HCA is d ssolved in benzene or other solvents. such. for example, as chlorobenzene. dicblorobenzene and chloroform and chlorinated in the com lete absen e of light but in the presence of a suspension of fullers earth the entire character of the product is changed. Repeatedtests have confirmed the fact that the chlorination mixture obtained from the adduct HCA in this fashion is at least twice as active an insect toxicant as the original CmHsCla mixture now known as Chlordane. We have also discovered that from this mixture a out can be obtained; by simple fractionation in vacuo re resenting approximately 25% of the total reaction mixture which solidifies and possesses insecti idal activity equal to or greater than that of hepta-chlor and from" which lar e quantities of hepta-chlor can be isolated by simple crystallization from methanol. These facts are alto ether unexpected not only in view of the results which had previously been obtained in numerous studies of the chlorination of the adduct HCA but parti ularly because of the wide variation of our results from those obtained by Bluestone,Taiima and Lidov in their previously cited dark chlorination of'the adduct exactly one gram atom of chlorine per mole of hepta-chlor treated; it removes no chlorine whatsoever from either of the known ODD isomers.

When our new chlorinated HCA composition is studied using the hereinabove described analytical tools it appears likely that the activity of this new composition is notsolely the result of its apparently enhanced hepta-chlor content. The

qualified "apparently enhanced" is necessary because at this time it is not possible to determine with certainty whetherthe isolation of heptachlor from our new chlorinated mixture is possible because of its presence in enhanced amounts or simply because the nature of the concomitant materials has now changed in such fashion as to permit hepta-chlor to be isolated and separated from them. The results so far obtained make it appear probable that the presence of fullers earth has not only altered the relative proportions of the previously known materials present but also has led to the formation of some of the theoretically possible but hitherto unknown isomers f the substances.

The formation of our new chlorinated adduct HCA composition. is but little aflected by variations either in the temperature at which chlorination is conducted or by changes in the concentration of the adduct solutions used. As a result, material can be prepared with substantially equal facility at any point within the temperature range of 30-100 C. Similarly the solution or the adduct HCA which is chlorinated can present for optimum results is however somewhat HCA in benzene solution in the presence or ab-' sence of carbon.

The empirical formula for our new chlorinated com osition (which will hereinafter be called NCC) lies between CmHeCla and C10H5C17, and appears to vary somewhat from batch to batch. Numerous previous studies have shown that differentiations are possible between the various CioHsCla isomers and between these isomers and the related compounds containinz seven and nine chlorine atoms on the basis of the reactivity of the chlorine atoms. Thus. when these various compounds are treated with 0.5N potassium hydroxide in isopro yl alcohol at the reflux. temperature of the solution for a period of an hour theyvary in the number of gram atoms of chlo-' rinewhich', under these conditions, can be re-' moved perlmole of compound treated. It is now known that under these conditions the new.

b-ODD loses only one gram atom of chlorine per mole of compound. The older a-ODD. on the other hand, loses, under identical conditions,

1.8 to 2 gram atoms of chlorine per mole of com- Similarly the compoundv hepta-chlor pound. loses between 3.5 and 3.7 gram atoms of chlorine per mole of compound and the crystalline compound CmHsCls loses, under similar circum more critical. Studies to date indicate that the "amount of fullers earth used should be not less than one-half per cent nor more than five per cent by weight of the amount of the adduct HCA present in the benzene solution and optimal results are obtained when the per cent of fullers earth present is within the range of one to three per cent. It has also been noted that with reduced amounts of fullers earth the quality of the product obtained increases as the chlorination rate is reduced so that for amounts of fullers earth less than those which are optimal some compensation can be obtained by reducing the rate of chlorination. In general, we prefer to employ one per cent of fullers earth and to chlorinate at a rate which leads to completion of the reaction within six to eight hours.

The examples which follow more specifically illustrate the methods. which can be employed in preparing our new chlorinated adduct HCA composition and the procedures which can be used in order to obtain crystalline hepta-chlor.

Example I illustrates the preparation of the starting material HCA.

EXAMPLE I To 64.5 grams of hexachlorocyclopentadienewas added 17.5 grams of cyclopentadiene and the mixture was mechanically stirred in a closed glass vessel fitted with an efflcient reflux condenser and a thermometer. The reaction is exothermic and the reacting mixture was cooled when its temperature reached C. After the initial exothermic reaction subsided, the reaction mixture was permitted to stand at room temperature un- 76 til solidification was complete. The solid was v then transferred to a suction funnel and dried by drawing air through it. There was thus obtained 79.9 grams of a white powdery solid of good quality. This material was further purified by recrystallization from methanol. The recrystallized compound was obtained as a white crystalline solid melting between about 170 and about 180 C.

Example 11 illustrates one method of preparing our new chlorinated HCA composition by the direct chlorination of the adduct HCA.

EXAMPLE II A one liter three necked flask was fitted with a reflux condenser, a motor-driven stirrer, and a sintered glass inlet tube. The apparatus set-up thus obtained was then carefully covered with an opaque black paint and with black friction tape in order to prevent the entrance of all light. Particular attention was given to the edges of the tubular glass apparatusplaced in the necks of the flask in order to preclude the entrance of light by transmission lengthwise through such apparatus. Into the apparatus thus prepared was placed a solution containing 200 grams of the adduct HCA dissolved in approximately 600 cc. of

benzene; two grams of fullers earth was suspended in this solution. The solution was heated to and maintained at reflux and chlorine was then introduced through the 'gas inlet tube at such a rate as to cause completion of the chlorination An apparatus set-up similar to that described in Example II above, except for the substitution of a five liter flask for the one liter flask there employed, was used for this preparation. There was placed in the light-tight flask a solution containing 1200 grams of the adduct HCA dissolved in 3.6 liters of benzene; 12 grams of fullers earth was suspended in this solution. The solution was heated to and maintained at its boiling point and the introduction of chlorine was commenced at a rate sufficient to effect chlorination of the adduct in a seven hour period. The reaction mixture was withdrawn from the flask, the fullers earth was separated on a filter and the solvent was removed from the chlorinated reaction product. There was thus obtained a nearly colorless viscous liquid which did not crystallize. The crude product thus obtained was subjected to rough fractionation in vacuo and the first twenty-five per cent by weight which distilled was separated; the fraction obtained in this manner solidified to give a yellow translucent mass. This crude solid was dissolved in methanol and at the boiling point of the methanolic solution treated with decolorizing charcoal and subsequently separated therefrom by filtration. The filtrate deposited white crystals which after separation on a filter and drying melted at approximately 80 C. This solid after one recrystallization from methanol melted at 6 92-94 C. and a mixture thereof with an authentic sample of hepta-chlor showed no melting point depression. The total weight of pure hepta-chlor thus obtained was approximately twenty per cent of that of the crude chlorination mixture. The procedures illustrated by the preceding examples can of course be modified in many ways without unduly altering the results obtained. It should therefore be clearly understood that these examples are illustrative only and are not in any fashion to be taken as limiting the scope of our invention.

The new composition of matter, NCC, which we have discovered is highly toxic to insect life. The high degree of insecticidal toxicity which this new compound possesses is particularly unexpected in view of the fact that no previously known chlorination mixture obtained by chlorinating the adduct HCA has approached our new composition NCC in insecticidal activity. The

- usefulness of our new NCC is further enhanced by the fact that it is highly soluble in a wide in high concentrations in liquid aliphatic and aromatic hydrocarbons, esters, ethers, ketones and other similar solvents.

The data hereinbelow set forth illustrates a high degree of toxicity which the new compound NCC possesses. The level of insecticidal activity is denoted by a number called the toxicity index which may be defined as one-hundred times the numerical value of the fraction which is obtained when the weight of compound undergoing test required to produce a given percentage mortality is divided into the weight of material used as a standard required to produce that same mortality. In general, therefore, the higher the toxicity index the greater the insecticidal activity of the compound. A compound equal in activity to the standard employed will have a toxicity index of less active compounds have indices with numerical values below 100 and more active compounds have toxicity indices above 100. In the data given below comparisons are made on the basis of the quantity of material required to produce a fifty per cent mortality.

Table I presents the results obtained when our new NCC is tested in comparison with Chlordane and a-ODD using the common housefly (Musca domestica) as the test insect and using the Kearns modified small chamber test (Soap and Sanitary Chemicals, May 1948, page 133).

Table I Compound: Toxicity index 1. Chlordane (standard) 100 2. (l-ODD 50 3. NCC of Example II 203 4. NCC of Example III 203 Examination of the data in Table I strikingly reveals the superiority of our new NCC as an insect toxicant.

Evaluation of the toxicity of the new NCC to other insect species likewise demonstrates the 7 superior insecticidal activity of this material.

Thus, using the German roach as the test insect the new NCC is found to have a toxicity index of approximately 200 when compared with Chlordane as the standard. Similarly, compared under the same conditions with Chlordane as a toxicant for the milkweed bug the new NCC is found to be approximately two to three times as effective as is Chlordane against this insect species.

Our new composition of matter, NCC, can be uitilized as an insect toxicant in all the ways 7. customary in the art. Thus it can be dissolved in the insecticide base oils normally employed (as was done to obtain the data of Table I) and the resulting solutions sprayed or otherwise employed in the usual fashion. It can also be combined with finely divided carriers to produce both propertes and other desirable characteristics. -Moreover, our new compound NCC can be incorporated in paints and other surface coatings in order to impart insecticidal characteristics to the surface finishes, it can be incorporated into waxes and wax emulsions in order that the surfaces treated with these materials may be made insecticidal, it can be incorporated into paper and into cardboard, into inks, into plasticizers,

into plastic sheets, etc. in order that desirable insecticidal characteristics can be acquired either directly by these materials or by the materials with which they are used.

It will be apparent to those skilled in the art that our new NCC which we have invented will have many uses other than those already enumerated. Thus, for example, it may because of its high solubility have value as a plasticizer and as a tackifier in many types of resinous and polymer compositions. This composition is also valuable as a starting compound and as an intermediate for perfumes, medicinals, fungicides and other organic compounds useful in the arts and sciences.

Moreover, modifications of the basic concept of our invention here presented will be evident to those skilled in the art. Such modifications are properly to be included within the scope of our disclosed invention which is, in no way, to be restricted by the various illustrative data hereinbei'ore contained but only by the claims appended hereto.

we claim:

1. The process for making the compound heptachlor which comprises the chlorination with elemental chlorine of 4, 5, 6, 7, 8, 8-hexachloro-3a,

. 4, 7, 7a-tetrahydro-4, 7-methanoindene dissolved in a solvent, in the presence of fullers earth suspended in the solution while the latter is maintained in complete darkness at a temperature between 30 and 100 0., separating the suspended fullers earth from the solution, and removing the solvent from the chlorinated product.

8 3. The process for making the compoun heptachlor which comprises the chlorination with elementalchlorine of 4, 5, 6, 7, 8, 8-hexachloro-3a. 4, 'z, 7a-tetrahydro-4, 7-methanoindene dissolved in a solvent, in the presence of fullers earth suspended in the solution while the latter is maintained in complete dapkness at a temperature between 30 and C., separating the suspended fullers earth fr the" solution, removing the solvent from the chlorinated product, distilling the chlorinated product, in vacuo, to separate the lower boiling portion thereof, and by fractional crystallization preparing substantially pure heptachlor from the crude heptachlor distillate so obtained.

4. A process according to claim 1, in which the solvent is selected from the group consisting of benzene, chlorobenzene, dichlorobenzene and chloroform.

5. A process according to claim 4, in which the amount of fullers earth employed varies between about one-half percent and about five percent based on the weight of 4, 5, 6, 7, 8, 8-hexachloro- 3a, 4, 7, 7a-tetrahydro-4, 7-methanoindene subjected to chlorination.

6. A process according to claim 5, in which the solvent is benzene.

7. A process according to claim 2, in which the solvent is selected from the group consisting of benzene, chlorobenzene, dischlorobenzene and chloroform.

8. A process according to claim 7, in which the amount of fullers earth employed varies between about one-half percent and about five percent based on the weight of 4, 5, 6, 7, 8, 8=hexachloro- 3a, 4, 7, 7a-tetrahydro-4, 7-methanoindene subjected to chlorination. A

9. A process according to claim 8, in which the solvent is benzene.

10. A process according to claim 3, in which the solvent is selected from the group consisting of benzene, chlorobenzene, dichlorobenzene, and chloroform.

11. A process according to claim 10, in which the amount of fullers earth employed varies between about one-half percent and about five percent based on the weight of 4, 5, 6, 7, 8, 8- 'hexachloro-3a, 4, 7, 7a-tetrahydro-4, 7-methanoindene subjected to chlorination.

12. A process according to claim -'ll, in which the solvent is benzene.

' HENRY BLUESTONE.

REX EVERE'I'I LIDOV. JAMES HARVEY KNAUS. PAUL WILLIAM HOWERTON.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS Number Country Date 618,432 Great Britain Feb. 22, 1949 OTHER REFERENCES Kearns et al.: J. Econ. Ent., vol. 42, No. 1, February 1949, pages 127-134. 

1. THE PROCESS FOR MAKING THE COMPOUND HEPTCHLOR WHICH COMPRISES THE CHLORINATION WITH ELEMENTAL CHLORINE OF 4,5,6,7,8,8-HEXACHLORO-3A, 4,7,7A-TETRAHYDRO-4,7-METHANOINDENEDISSOLVED IN A SOLVENT, IN THE PRESENCE OF FULLER''S EARTH SUSPENDED IN THE SOLUTION WHILE THE LATTER IS MAINTAINED IN COMPLETE DARKNESS AT A TEMPERATURE BETWEEN 30* AND 100* C., SEPARATING THE SUSPENDED FULLER''S EARTH FROM THE SOLUTION, AND REMOVING THE SOLVENT FROM THE CHLORINATED PRODUCT. 